Liquid crystal compositions

ABSTRACT

A liquid detergent composition which is in liquid crystal form comprises a synthetic organic surface active agent, as the detergent component, which preferably includes one or more nonionic detergents of the ethoxylated higher fatty alcohol type, and a lesser proportion of anionic or cationic surfactant, such as sodium dialkyl sulfosuccinate or dicoco dimethyl ammonium chloride, a cosurfactant, such as tripropylene glycol butyl ether, a solvent for the soil, such as an isoparaffin of 9 to 11 carbon atoms or methyl cocoate (ester of methyl alcohol and coco acids) and water, with the water usually being the major component. Such compositions are useful for cold or room temperature cleaning of lipophilic soils, such as animal fats, from hard surfaces and from fabrics, and may be used as pre-treatments to loosen such soils from substrates to facilitate easier cleaning of dishes and laundry with conventional or the invented detergent compositions. 
     The invention also relates to concentrated versions of the compositions, which are not in liquid crystal state but which upon dilution with water are converted to such state. Also within the invention are processes for pre-treating and cleaning materials soiled with lipophilic soils, using the invented liquid crystal detergent compositions. Additional processes of the invention are those in which liquid crystal detergent compositions are made by diluting concentrated compositions with water, and those in which lipophilic materials convert liquid crystal detergent compositions to microemulsion form, which latter processes occur during pre-spotting and cleaning applications when the liquid crystal detergent composition contacts the oily soil on surfaces being treated.

This application is a continuation-in-part of application Ser. No.8/096,501 filed on Sep. 3, 1993, now abandoned which is a continuationof application Ser. No. 07/726,597, filed Jul. 8, 1991 which in turn isa continuation application of U.S. Ser. No. 07/411,280 filed Sep. 22,1989 U.S. Pat. No. 5,035,826, granted Jul. 30, 1991.

This invention relates to a liquid crystal detergent composition. Morespecifically, it is of a liquid detergent composition in liquid crystalstate or form, which by virtue of its liquid crystal nature and readyconvertibility to a microemulsion when brought into contact with oilysoil, is superior to other liquid detergent compositions in detergencyand in other physical properties.

Liquid aqueous synthetic organic detergent compositions have long beenemployed for human hair shampoos and as dishwashing detergents for handwashing of dishes (as distinguished from automatic dishwashing machinewashing of dishes). Liquid detergent compositions have also beenemployed as hard surface cleaners, as in pine oil liquids, for cleaningfloors and walls. More recently they have proven successful as laundrydetergents too, apparently because they are convenient to use, areinstantly soluble in wash water, and may be employed in "pre-spotting"applications to facilitate removals of soils and stains from laundryupon subsequent washing. Liquid detergent compositions have comprisedanionic, cationic and nonionic surface active agents, builders andadjuvants, including, as adjuvants, lipophilic materials which can actas solvents for lipophilic soils and stains. The various liquid aqueoussynthetic organic detergent compositions mentioned serve to emulsifylipophilic materials, including oily soils, in aqueous media, such aswash water, by forming micellar dispersions and emulsions.

Although emulsification is a mechanism of soil removal, it has been onlycomparatively recently that it was discovered how to make microemulsionswhich are much more effective than ordinary emulsions in removinglipophilic materials from substrates. Such microemulsions are describedin British Patent Specification No. 2,190,681 and in U.S. Pat. Nos.5,075,026; 5,076,954; 5,082,584; and 5,108,643, most of which relate toacidic microemulsions useful for cleaning hard surfaced items, such asbathtubs and sink, which microemulsions are especially effective inremoving soap scum and lime scale from them. However, as in U.S. Pat.No. 4,919,839, the microemulsions may be essentially neutral and suchare also taught to be effective for microemulsifying lipophilic soilsfrom substrates. In U.S. patent application Ser. No. 07/313,664 there isdescribed a light duty microemulsion liquid detergent composition whichis useful for washing dishes and removing greasy deposits from them inboth neat and diluted forms. Such compositions include complexes ofanionic and cationic detergents as surface active components of themicroemulsions.

The various microemulsions referred to include a lipophile, which may bea hydrocarbon, a surfactant, which may be an anionic and/or a nonionicdetergent(s), a co-surfactant, which may be a poly-lower alkylene glycollower alkyl ether, e.g., tripropylene glycol monomethyl ether, andwater.

Although the manufacture and use of detergent compositions inmicroemulsion form significantly improves cleaning power and greasy soilremoval, compared to the usual emulsions, the present invention improvesthem still further and also increases the capacity of the detergentcompositions to adhere to surfaces to which they have been applied.Thus, they drip or run substantially less than cleaning compositions of"similar" cleaning power which are in microemulsion or normal liquiddetergent form. Also, because they form microemulsions with lipophilicsoil or stain material spontaneously, with essentially no requirementfor addition of any energy, either thermal or mechanical, they are moreeffective cleaners at room temperature and at higher and lowertemperatures that are normally employed in cleaning operations than areordinary liquid detergents, and are also more effective than detergentcompositions in microemulsion form.

The present liquid crystal detergent compositions may be either clear orsomewhat cloudy or milky (lactescent) in appearance but both formsthereof are stable on storage and components thereof do not settle outor become ineffective, even on storage at somewhat elevated temperaturesfor periods as long as six months and up to a year. The presence of thecosurfactant in the liquid crystal detergent compositions helps to makesuch compositions resist freezing at low temperatures. Another advantageof the present invention, in another aspect of it, is that the inventedliquid crystal detergent compositions can be produced from moreconcentrated microemulsions by dilution with water, without the additionof any significant amount of energy, and such concentrates, being inmicroemulsion form, are also stable on storage. Thus, if desired, theconcentrate may be marketed to save shipping costs and storage space,and the consumer may effect the dilution (or may employ the concentratedirectly).

In accordance with the present invention a liquid detergent composition,suitable at room temperature or colder, for pre-treating and cleaningmaterials soiled with lipophilic soil, is in liquid crystal form or iscapable of being diluted with water and thereby being converted toliquid crystal form, and comprises a synthetic organic surface activeagent, a cosurfactant, a solvent for the soil, and water. The inventionalso relates to processes for treating items and materials soiled withlipophilic soil, with compositions of this invention, to loosen orremove such soil, by applying to the locus of such soil on such materiala soil loosening or removing amount of an invented composition. Theinvention is also in converting a concentrated liquid detergentcomposition of the invention, normally in microemulsion form, to aliquid crystal composition by addition of water thereto and halting thewater addition when the formula of the diluted detergent is in in theliquid crystal range (as it appears on awater-oil-surfactant/cosurfactant phase diagram). In another aspect ofthe invention lipophilic soil is absorbed from the soiled surface intothe liquid crystal, and such absorption converts the liquid crystal tomicroemulsion form, or after such absorption of the lipophilic soil theliquid crystal is converted to microemulsion form by further addition ofwater.

The nonionic and ionic surfactants and synthetic organic detergents thatare employed in the invented cleaning compositions are preferably watersoluble but such materials that are water dispersible can also be used.The soluble nonionic compounds are usually condensation products of anorganic aliphatic or alkylaromatic hydrophobic compound and a loweralkylene oxide, such as ethylene oxide, which is hydrophilic. Almost anyhydrophobic compound having a carboxy, hydroxy, amido or amino groupwith a free hydrogen present can be condensed with ethylene oxide orwith polyethylene glycol to form a nonionic detergent. The length of thepolyethenoxy chain of the condensation product can be adjusted toachieve the desired balance between the hydrophobic and hydrophilicelements (hydrophilic-lipophilic balance, or HLB).

Particularly suitable nonionic detergents are the condensation productsof a higher aliphatic alcohol, such as a fatty alcohol, containing about8 to 18 or 20, more preferably 8 to 12 carbon atoms, in a straight (orbranched) chain configuration, condensed with about 2 to 30, preferably2 to 10, and more preferably 2 to 6 and most preferably 2.5 to 5 molesof ethylene oxide. Particularly preferred such compounds are C₉₋₁₁alkanol ethoxylates of five moles of ethylene oxide per mole (5 EtO),which also may be designated as C₉₋₁₁ alcohol EO 5:1, and C₉₋₁₁ alkanolethoxylates of 2.5 moles of ethylene oxide per mole (C₉₋₁₁ alcohol EO2.5:1), and mixtures thereof. Narrow range ethoxylates (NRE's) ofsimilar types may be used instead of the described broad rangeethoxylates (BRE's).

Other suitable nonionic detergents are the polyethylene oxidecondensates of one mole of alkyl phenol containing from about 6 to 12carbon atoms in a straight- or branched-chain configuration, with about2 to 30, preferably 2 to 15 moles of ethylene oxide, such as nonylphenol condensed with 9 moles of ethylene oxide, dodecyl phenolcondensed with 15 moles of ethylene oxide, and isooctyl phenol condensedwith 15 moles of ethylene oxide. These aromatic compounds are not asdesirable as the aliphatic alcohol ethoxylates in the inventedcompositions because they are not as biodegradable.

Another well known group of usable nonionic detergents is marketed underthe trade name "Pluronics". These compounds are block copolymers formedby condensation of ethylene oxide with a hydrophobic base formed by thecondensation of propylene oxide with propylene glycol. The molecularweight of the hydrophobic portion of the molecule is of the order of 950to 4,000, preferably 1,200 to 2,500. The condensation of ethylene oxidewith the hydrophobic moiety increases the water solubility of thehydrophobe. The molecular weight of these polymers is in the range of1,000 to 15,000, and the polyethylene oxide content may comprise 20 to80% thereof.

Still other satisfactory nonionic detergents are condensation productsof a C₈₋₁₆ alkanol with a heteric mixture of ethylene oxide andpropylene oxide. The mole ratio of ethylene oxide to propylene oxide isfrom 1:1 to 4:1, preferably from 1.5:1 to 3.0:1, with the total weightof the ethylene oxide and propylene oxide contents (including theterminal ethanol group or propanol group) being from 60% to 85%,preferably 70% to 80%, of the molecular weight of the nonionicdetergent. The higher alkanol may contain 9 or 11 to 12 or 15 carbonatoms and one such nonionic detergent is the condensation product ofC₁₃₋₁₅ alkanol with 4 moles of propylene oxide and 7 moles of ethyleneoxide, which is available from BASF Corp. under the trade name PlurafacLF400.

Also suitable for incorporation in the invented cleaning compositionsare the nonionic detergents that are derived from the condensation ofethylene oxide with the product resulting from the reaction of propyleneoxide and ethylene diamine. For example, satisfactory such compoundscontain from about 40 to 80% of polyoxyethylene by weight, have amolecular weight of from about 5,000 to 11,000, and result from thereaction of ethylene oxide with a hydrophobic base which is a reactionproduct of ethylene diamine and excess propylene oxide, which base is ofa molecular weight in the range of 2,500 to 3,000.

Additionally, polar nonionic detergents may be substituted for thegenerally non-polar nonionic detergents described above. Among suchpolar detergents are those in which a hydrophilic group contains asemi-polar bond directly between two atoms, for example, N--O and P--O.There is charge separation between such directly bonded atoms, but thedetergent molecule bears no net charge and does not dissociate intoions. Suitable such polar nonionic detergents include open chainaliphatic amine oxides of the general formula R⁷ -R⁸ -R⁹ N--O, whereinR⁷ is an alkyl, alkenyl or monohydroxyalkyl radical of about 10 to 16carbon atoms and R⁸ and R⁹ are each selected from the group consistingof methyl, ethyl, propyl, ethanol, and propanol radicals. Preferredamine oxides are the C₁₀₋₁₆ alkyl dimethyl and dihydroxyethyl amineoxides, e.g., lauryl dimethyl amine oxide and lauryl myristyldihydroxyethyl amine oxide. Other operable polar nonionic detergents arethe related open chain aliphatic phosphine oxides having the generalformula R¹⁰ R¹¹ R¹² P--O wherein R¹⁰ is an alkyl, alkenyl ormonohydroxyalkyl radical of a chain length in the range of 10 to 18carbon atoms, and R¹¹ and R¹² are each alkyl or monohydroxyalkylradicals containing from 1 to 3 carbon atoms. As with the amine oxides,the preferred phosphine oxides are the C₁₀₋₁₆ alkyl dimethyl anddihydroxyethyl phosphine oxides.

The anionic surface active agents (or surfactants) will preferably bedetergents and will normally include a lipophilic anionic moiety orplurality of moieties of relatively high molecular weight, usually morethan 100, which lipophile(s) will preferably be or will include one ormore alkyl or alkenyl groups of at least six carbon atoms, such as 6 or8 to 12 or 18 carbon atoms, which are preferably alkyls. Such anionicdetergent will also usually include a neutralized sulfonic, sulfuric orcarboxylic acid group and preferably will include a neutralized sulfonicor sulfuric acid group (a neutralized carboxylic acid group may also bepresent in such detergents), with the cation thereof preferably beingalkali metal, ammonium or alkanolamine, such as sodium, potassium,ammonium or triethanolamine.

Examples of operative anionic surfactants include sodium dioctylsulfosuccinates [di-(2-ethylhexyl) sodium sulfosuccinate being one] andcorresponding dihexyl and didecyl esters; sodium dodecylbenzenesulfonate; sodium linear tridecylbenzene sulfonate; sodium laurylsulfate; triethanolamine lauryl sulfate; sodium cocoalkyl sulfate;sodium ethoxylated higher fatty alcohol sulfate, which will usually beof 1 to 20 ethylene oxide groups per mole, such as sodium laurylmonoethoxy ether sulfate, sodium lauryl diethoxy ether sulfate andsodium C₁₂₋₁₄ alkyl triethoxy ether sulfate; sodium C₁₄₋₁₇ paraffinsulfonate; sodium olefin sulfonate (of 10 to 20 carbon atoms in theolefin); and sodium cocomonoglyceride sulfate. These act to improveproduct stability at high temperatures.

The preferred sulfosuccinic acid ester salts are esters of aliphaticalcohols, such as saturated alkanols of 4 to 12 carbon atoms (preferably6 to 10, e.g., about 8) and are normally diesters of such alkanols. Morepreferably such are alkali metal salts of the diesters o alcohols of 6to 10 carbon atoms and most preferably the diesters will be of octanol,such as 2-ethyl hexanol, and the sulfonic acid salt will be the sodiumsalt.

As with the other ionic surfactants, the anionic surfactants, thecationic surfactants useful in the present invention, also preferablywith the nonionic detergent, will be of detersive properties, and it isconsidered that such ionic surfactants also improve and stabilize theliquid crystal state of the phase diagram liquid crystals at normal usetemperatures, such as 25°-50° C. Preferable among such cationicsurfactants are quaternary ammonium salts, in which at least one highermolecular weight group and two or three lower molecular weight groupsare linked to a common nitrogen atom to produce a cation, and whereinthe electrically balancing anion is a halide, acetate, nitrite or loweralkosulfate, such as bromide, chloride or methosulfate. The highermolecular weight substituent(s) on the nitrogen is/are often (a) higheralkyl group(s), containing 10 or 12 to 18 or 20 carbon atoms and thelower molecular weight substituents may be lower alkyl of 1 to 4 carbonatoms, such as methyl and ethyl, which may be substituted, as withhydroxy, in some instances. One or more of said substituents may includean aryl moiety or may be replaced by an aryl, such as benzyl or phenyl.Among the possible lower molecular weight substituents are also loweralkyls of 1 to 4 carbon atoms, such as methyl and ethyl, substituted bypoly-lower alkoxy moieties, such as polyethoxy moieties, bearing ahydroxyl end group, and being of the general formula R(X)_(n) OH whereinR is C₁₋₄ alkyl bonded to the nitrogen, X is CH₂ CH₂ O or CH(CH₃)CH₂),and n is from 1 to 20. Alternatively, one or two of such lowerpoly-lower alkoxy moieties, having terminal hydroxyls, may be directlybonded to the quaternary nitrogen instead of being bonded to it throughthe previously mentioned lower alkyl.

Among the useful quaternary ammonium halide surfactants are dilauryldimethyl ammonium chloride, dimyristyl diethyl ammonium chloride,di-tallowalkyl dimethyl ammonium chloride, lauryl trimethyl ammoniumchloride and cetyl trimethyl ammonium bromide, with the di-higher alkylsubstituted compounds being preferred over those which are onlymono-higher alkyl substituted.

In addition to the cationic compounds previously mentioned, othersuitable cationic surfactants include the imidazolinium salts, such as2-heptadecyl-1-methyl-1-[(2-stearoylamido)ethyl]-imidazolinium chloride;the corresponding methosulfate compound;2-methyl-1-(2-hydroxyethyl)-1-benzyl imidazolinium chloride; and2-heptadecyl-1-(hydroxyethyl)-1-octadecyl imidazolinium ethyl sulfate.Generally, the imidazolinium salts of preference will be halides(preferably chlorides) and lower alkosulfates, and may includehydroxy-lower alkyl substituents.

Preferably, the nonionic detergent will be accompanied by either ananionic or a cationic surfactant, preferably a detergent, with theamount of such ionic surfactant being less than that of the nonionicdetergent, which lesser proportion is sufficient to stabilize the liquidcrystal at room temperature and at higher and lower temperatures, suchas from 10° to 50° C.

The cosurfactant of the present liquid crystal compositions, whichsignificantly aids in the formations of such liquid crystals andmicroemulsions, is preferably a monoalkyl ether of a lower glycol orpolyalkylene glycol of the formula RO(X)_(n) H, wherein R is C₁₋₅ alkyl,X is CH₂ CH₂ O or CH(CH₃)CH₂ O), and n is from 1 to 5, or a mono- alkylester of the formula R¹ O(X)_(n) H, wherein R¹ is C₂₋₄ acyl and X and nare as immediately previously described. In the formula given X ispreferably a propoxy group and n is preferably 2 or 3, more preferably3.

Other amphiphiles may be substituted for the named cosurfactants, suchas those of 5 to 20 carbon atoms, which include a hydrogen-heteroatombond, with the heteroatom being of an electronegativity above 2.5 units.The amphiphile usually includes an --OH, --NH₂, --COOH or --CONH₂radical, and some examples of such cosurfactants are of 3 to 9 carbonatoms, corresponding to the glycol ethers named below, with NH₂, CONH₂and COOH replacing the free hydroxyls. Satisfactory glycol ethers andother glycol derivatives include tripropylene glycol mono-n-butyl ether,dipropylene glycol mono-n-butyl ether, dipropylene glycol isobutylether, pentapropylene glycol monobutyl ether, propylene glycol tertiarybutyl ether, diethylene glycol mono-n-butyl ether (butyl carbitol),ethylene glycol mono-butyl ether (butyl cellosolve), tetraethyleneglycol monobutyl ether, propylene glycol monoacetate and dipropyleneglycol propionate. Of the cosurfactants those which are preferred arethe mono-lower alkyl ethers 3 to 6, preferably 4 carbon atoms in suchalkyls) of mono-to penta-propylene glycols, preferably the normal butylethers, and most preferably tripropylene glycol mono-n-butyl ether(although the corresponding dipropylene compound is also verysatisfactory).

The organic solvent component of the present liquid crystals includessolvents for the soils, which solvents may have polar properties, oftenin minor proportions, but the preferred organic solvent is lipophilicand is a suitable oil, such as a non-polar oil, which is preferably ahydrocarbon of 6 to 16 carbon atoms. Such hydrocarbon is desirably anormal paraffin or an isoparaffin, and of these those which aresaturated and of 7 to 13 carbon atoms are preferred, with isoparaffinsof 8 to 12 carbon atoms being more preferred. The best are the C₉₋₁₁isoparaffins (which average such numbers of carbon atoms. Such materialsare available commercially from Exxon Corp. under the trade name IsoparH. In addition to such hydrocarbons, terpenes and similar perfumematerials may be employed, as described in British Patent SpecificationNo. 2,190,681. Other useful hydrocarbons are heptane, octane and nonanebut also included are those of cyclic structure, such as cyclohexane.Among other solvents that are useful are the lower (C₁₋₆) alkyl estersof higher (C₁₀₋₁₈) carboxylic acids, such as methyl cocoate, and/or thehigher (C₁₀₋₁₈) alkyl esters of lower (C₁₋₆) acids, such as laurylpropionate. Such compounds may be considered as representative of thegroups of useful oils of polar properties, and are useful solvents inthe invented compositions because of their similarity in structure tothe fats and oils that are to be removed from substrates by the inventedcompositions.

The last of the components of the invented liquid crystal compositionsis water and deionized water is preferably the form used, although tapwaters may also be employed, too, preferably of a hardness not in excessof 150 p.p.m., as CaCO₃.

In addition to the recited components of the compositions of the presentinvention there may also be present adjuvant materials for dishwashing,laundering and other detergency applications, which materials mayinclude: foam enhancing agents, such as lauric myristic diethanolamide;foam supressing agents (when desired), such as silicones, higher fattyacids, and higher fatty acid soaps; preservatives and antioxidants, suchas formalin and 2,6-ditert. butyl-p-cresol; pH adjusting agents, such assulfuric acid and sodium hydroxide; perfumes, colorants (dyes andpigments); and opacifying or pearlescing agents, if desired. In additionto the mentioned adjuvants, sometimes it may be desirable to includewater soluble metal salts, such as chlorides and sulfates of magnesiumand aluminum, to react with the anionic detergent to convert it to sucha metal salt, which may improve performance of the invented composition.Such salts normally work best at acidic or neutral pH's when they arepresent in the invented compositions.

In broad terms, the proportions of the components of the present liquiddetergent compositions, in liquid crystal form, are a detersiveproportion of synthetic organic surface active agent, a cosurfactantproportion of the cosurfactant, a proportion of solvent sufficient tohelp remove lipophilic soil from substrates, and enough water to placethe composition within the liquid crystal area of its phase diagram andto act as the continuous medium for the oil-in-water microemulsion to beformed from the liquid crystal during use. Preferred ranges ofproportions of the synthetic organic surfactant(s) are 5 to 40%,preferably 10 to 25% and more preferably 10 to 15%. Of the totalsurfactant content the proportion of ionic surfactant, either anionic orcationic, will be relatively small, normally being within the range of 2to 25% of the amount of nonionic detergent present, preferably 3 to 10%thereof. Preferably, the surfactant components of the invented liquidcrystal compositions will be nonionic and anionic detergents, inmixture, and in such mixture the nonionic detergent will be about 6 to35% of the composition, preferably 10 to 15% thereof and the anionicdetergent will be 0.3 to 5% of the composition, more preferably 0.5 to2% thereof. A most preferred content of nonionic detergent will be about12.5% and it will be a mixture of about 10% (or 9.9%) of an nonionicdetergent which is more hydrophilic, and about 2.5% of a nonionicdetergent which is less hydrophilic (degrees of ethoxylation of 5 and2.5, respectively).

The cosurfactant content in the liquid crystal compositions is normallyin the range of 0.5 to 20%, preferably being 2 to 15% and morepreferably being 5 to 10%, e.g., about 7%. For the purpose of theplotting of the phase diagram of the invented compositions thesurfactants and cosurfactant(s) will be considered together as onecomponent, with the water and the solvent being the other two. Theamount of cosurfactant will normally be about 5 or 10 to 50% of the sumof the amounts of surfactants and cosurfactant, with the sum of thesurfactants and cosurfactant amounts or percentages being about 5 or 10to 60% of the composition. Preferred such percentages are 20 to 45% and10 to 40%, respectively, with more preferred percentages being 30 to 40%and 15 to 25%, respectively.

The solvent content of the liquid crystal compositions will normally be1 to 20% thereof, preferably 2 to 10% and more preferably 3 to 7%, e.g.,about 5%, and the water content will normally be in the range of about40 to 90%, preferably 50 to 85% and more preferably 60 to 80%, e.g.,75%. Adjuvants, which are optional components, will normally not exceed15% of the composition and will preferably not include any non-enzymaticmaterials having molecular weights above 5,000 (because such highmolecular weight compounds interfere with the preparation of the presentcompositions and their maintenance in the liquid crystal state).Enzymes, which may have such higher molecular weights, can be toleratedin the detergent compositions but normally the proportion of enzyme willbe held to no more than 2% and preferably will be less than 1% of thecomposition to avoid any interference with the liquid crystal. The totalproportion of adjuvants will be in the range of 0 to 15%, preferably 0to 10%, more preferably 0 to 5%, and most preferably will be no morethan 2%.

The concentrates of this invention, which upon dilution with up to threeparts of water, preferably from 0.25 to 2 parts, per part ofconcentrate, result in creation of a liquid crystal, are of compositionsdetermined by the previously recited proportions of components for theliquid crystal compositions, and the dilution to be effected. Of course,the concentrates will contain less water but the relative proportions(not percentages) of the other components will be kept in the sameranges as previously recited. The concentrates will usually be inmicroemulsion form and when the requisite amount of water is added tothem, will be spontaneously converted to liquid crystals. Because of theprevious recitations of proportions of components in the liquid crystalcompositions and the evident relationship between the compositions ofthe concentrates and the liquid crystal detergent compositions made fromthem it is not considered to be necessary to recite here specific rangesof proportions for usual, preferred, more preferred and most preferredcompositions. Such are readily calculable from the correspondingpercentages given for the desired liquid crystal detergent. However,such concentrated liquid detergent composition which is in microemulsionform and which will yield a liquid crystal upon dilution with water, notexceeding three parts of water per part of the concentrated composition,comprises a nonionic detergent, preferably with an anionic detergent, acosurfactant which is an organic amphiphile of 1 to 10 carbon atoms thatincludes a hydrogen-heteroatom bond, with the heteroatom being of anelectronegativity above 2.5 units, a lipophilic solvent and water. Aspecific preferred concentrated liquid detergent composition comprisesabout 12.5 parts of nonionic detergent (preferably a mixture of two suchdetergents of different formulas and hydrophilicities with both being ofa higher fatty alcohol of 9 to 11 carbon atoms condensed with 2 to 6moles of ethylene oxide, about 0.7 part of sodium C₆₋₁₀ dialkylsulfosuccinate, about 7 parts of tripropylene glycol lower alkylmonoether, wherein the lower alkyl is of 3 to 6 carbon atoms, about 5parts of paraffin or isoparaffin of an average of 9 to 11 carbon atoms,0 to 5 parts of adjuvants and up to 50% of the concentrated compositionof water, with the proportion of water preferably being in the range of5 to 40% and more preferably 10 to 30%. For example, a concentratecontaining 60% of surfactant-cosurfactant system of the type described(nonionic detergent/sulfosuccinate/tripropylene glycol n-butyl ether),15% of isoparaffin and 25% of water, when diluted with two parts ofwater per part of concentrate, will be converted from microemulsionform, during dilution, first to a cloudy or turbid liquid crystal andthence to a clear liquid crystal, with the final composition analysisbeing 20% of the surfactant-cosurfactant system, 5% of the isoparaffinand 75% of water.

The phase transformations between concentrates and liquid crystals, andbetween liquid crystals and microemulsions resulting from use of theinvention, and the variations in formulas of compositions within theinvention which are in liquid crystal state, are easily ascertainableand the invention is readily understood when reference is made to thisspecification, including the working examples thereof, taken inconjunction with the drawing, in which:

FIG. 1 is a phase diagram, showing both clear and turbid liquid crystalcomposition areas for preferred compositions of this invention, in whichthe cosurfactant is tripropylene glycol n-butyl ether, the surfactantsinclude higher fatty alcohol condensates with ethylene oxide, asnonionic detergent(s), and sodium dioctyl sulfosuccinate, as anionicdetergent, and the lipophile is an isoparaffin of 9 to 11 carbon atoms;and

FIG. 2 is a related phase diagram wherein the co-surfactant is propyleneglycol n-butyl ether.

In FIG. 1 phase diagram 11 includes area 13 which defines the clearliquid crystal compositions, and area 15, which defines the turbid orlactescent liquid crystals. Area 17, defined by line 19 and the zeropercent surfactant-cosurfactant system line 21 is where the compositionis an emulsion, dispersion or other plural phase type.

For illustration, the composition at point 23, marked by the X, is of75% water, 20% surfactant-cosurfactant system and 5% paraffin(isoparaffin). When such composition is brought into contact withlipophilic soil and "absorbs it" in effect the paraffin or lipophilecontent at the interface is increased and the composition becomes amicroemulsion, leaving the liquid crystal area of the phase diagram. Ina related type of transformation of phases, the microemulsion identifiedby the location of the X at 25 of the phase diagram, which is aconcentrated water-in-oil microemulsion, when diluted with two parts ofwater per part of the microemulsion, is transformed into a clear liquidcrystal composition identified by the X at numeral 23. However, when thedilution of the concentrate is with only one part of water per fourparts of concentrate the composition resulting is a turbid liquidcrystal, of the formula defined by location 27. By further dilutions ofsuch liquid crystal with water other such turbid liquid crystalcompositions can be produced, as well as other transparent liquidcrystal composition up to and beyond the composition indicated at 23.Subsequent dilution of the clear liquid crystal will convert it tomicroemulsion form and ultimately to other plural phase form.

In FIG. 2 phase diagram 29 is shown to include cross-hatchedmicroemulsion area 31, in which is located a concentrated composition ata location marked by an X, which location is identified by numeral 33.Also shown is white liquid crystal area 35, in which is located apreferred liquid crystal composition of the invention at the Xidentified by numeral 37. An emulsion (or non-microemulsion andnon-liquid crystal) area 39, which is white in the figure, is alsoidentified. The microemulsion concentrate composition 33, upon dilutionwith two parts of water per part of composition, is converted to theliquid crystal 37. Similar phase diagrams, like those of FIGS. 1 and 2,may be drawn for other three-member compositions comprising water,lipophile and surfactant-cosurfactant systems within the invention andeach will include liquid crystal, microemulsion and "other phases"areas.

In the previous description of the components of the inventedcompositions and proportions thereof which may be operative, boundarieswere drawn for preferred compositions within the invention but it willbe evident that one seeking to manufacture the invented liquid crystalcompositions and concentrates that produce them upon dilution with waterwill select proportions of components indicated by the phase diagramsfor the particular compositions, so that the desired compositions willbe within the liquid crystal area and the concentrates will be such thatdilution with water will result in compositions within the liquidcrystal area. Similarly, the compositions selected should be such thatupon contact with lipophilic soil to be removed from a substrate theinterface composition will be a microemulsion, rather than an "ordinary"emulsion, for best soil removal activity. Thus, for example, referenceto FIG. 1 indicates that the microemulsion will be more readily formedwhen the liquid crystal composition contacts the lipophilic soil if theliquid crystal is of a composition on the lower left side of the clearliquid crystal area, rather than at the upper right portion thereof.

For plotting of the phase diagrams and in experiments undertaken by theinventors to establish the formulas of the desired liquid crystalcompositions many different compositions within the invention were madeand were characterized, by observations of certain properties, as clearliquid crystals, turbid liquid crystals, microemulsions or "others" andon the bases of such observations the phase diagrams were drawn, eitherby hand (FIG. 1) or by computer (FIG. 2).

A composition of this invention is in a liquid crystal state when it isof lyotropic structure, is transparent or slightly turbid (lactescent)but not opaque, and has a storage modulus equal to or higher than onePascal (1 Newton/sq. m.), when measured at a temperature of 25° C., at afrequency of ten radians per second and a strain of 0.01. Therheological behavior of such composition is measured by means of aRheometrics Fluids Spectrometer 8400, manufactured by RheometricsCompany, Piscataway, N.J. In making the measurement, using the coaxialcylinders, the inner cylinder, which is fixed, is of a radius of 16 mm.and a height of 32 mm., and the outer cylinder, which is mobile, is of aradius of 17 mm.

The storage modulus for the compositions of Examples 1 and 2, asidentified in FIGS. 1 and 2, is 2.7 Pascals. The preferred clearlyotropic liquid crystal of the invention is of undulating lamellae,with a corelation length below 1,000 Å. The lamellar liquid crystallinephase may be regarded as a packing of soft wave shaped membranes. Thesystem is composed of a succession of thin oil-containing layers thatare separated by water layers, with surfactant at the interfaces of thelayers.

It is desirable that the invented compositions do not contain componentsof the molecular weights above 5,000 but in some instances, as when thecomposition exhibits physical and cleaning properties that are verydesirable in a successful pre-spotting agent, the presence of suchhigher molecular weight components may be tolerated. Also, sometimesenzymatic components may be employed which can be of molecular weightshigher than 5,000, in some forms, and the importance of the enzymaticaction in loosening soils and cleaning substrates counterbalances thedisadvantages of the presence in the composition of the higher molecularweight material.

To make the liquid crystal compositions of the invention is relativelysimple because they tend to form spontaneously with little need for theaddition of energy to promote transformation to the liquid crystalstate. However, to promote uniformity of the composition mixing willnormally be undertaken and it has been found desirable first to mix thesurfactants and cosurfactant with the water, followed by admixing of thelipophilic component, usually a hydrocarbon (but esters or mixtures ofhydrocarbons and esters may also be employed). It is not necessary toemploy heat and most mixings are preferably carried out at about roomtemperature (20°-25° C.). The microemulsion concentrates, from which theliquid crystal compositions may be made by dilution with water, are alsomanufactured according to the same procedure and the liquid crystalcompositions are made from the concentrates merely by dilution withwater, accompanied by sufficient mixing to make the final producthomogeneous.

Pre-spotting and cleaning uses of the invented liquid crystal detergentcompositions are uncomplicated, requiring no specific or atypicaloperations. Thus, such compositions may be employed in the same manneras other liquid pre-spotting and detergent compositions. Because thetransformation to microemulsion state from liquid crystal state byabsorption of lipophilic soil is spontaneous and occurs at roomtemperature (and even at colder temperatures) it is not necessary toheat the liquid crystal compositions nor the subtrate before applicationof the liquid crystal detergent (or pre-spotting agent) to the surfaceto be cleaned. The invented compositions may be applied to such surfacesby pouring onto them, by application with a cloth or sponge, or byvarious other contacting means but it is preferred to apply them in theform of a spray by spraying them onto the substrate from a hand orfinger pressure operated sprayer or squeeze bottle. Such application maybe onto hard surfaces, such as dishes, walls or floors, from whichlipophilic (usually greasy or oily) soil is to be removed, or may beonto fabrics, such as laundry, which has previously been stained withlipophilic soils, such as motor oil. The invented compositions may beused as detergents and as such may be employed in the same manner inwhich liquid detergents are normally utilized in dishwashing, floor andwall cleaning and laundering, but it is preferred that they be employedas pre-spotting agents too, in which applications they are found to beextremely useful in loosening the adhesions of lipophilic soils tosubstrates, thereby promoting much easier cleaning with application ofmore of the same invented detergent compositions or by applications ofdifferent commercial detergent compositions, in liquid, bar orparticulate forms. As was previously indicated, the liquid crystalcompositions spontaneously convert to microemulsions upon contact withlipophilic soil and such microemulsion formation effectively weakens thebond of the soil to the substrate. After it is in the microemulsion thesoil is readily transferred to aqueous washing or rinsing media, whichmakes it very easily removable from the substrate. The absorption of thelipophilic soil by the liquid crystal detergent composition isaccompanied by a change in the nature of the composition. The liquidcrystal detergent is of a greater viscosity and adhesion than is themicroemulsion, to which it is converted by absorption of the lipophile.Thus, when sprayed onto a surface, such as a vertical wall, the presentcleaning compositions adhere to it and do not run or drip excessively,thereby allowing the detergent to work on the lipophilic soil moreeffectively. When the transformation to microemulsion form has takenplace a sign of it will be thinning of the product and running down ofthe microemulsion from the original locus of application. The thinningalso facilitates removal of the detergent composition from the substrateby sponging, rinsing, etc. While the advantages of a thicker and moreadhering liquid detergent composition are more significant for wallcleaning than for dishwashing, floor cleaning or laundering, even in thecases of such horizontal surfaces or surfaces which can be maintainedhorizontal, the applied liquid crystal detergent compositionsubstantially remains at the locus of the lipophile and thereby isbetter able to perform its cleaning function.

The following examples illustrate but do not limit the invention. Unlessotherwise indicated, all parts in these examples, in the specificationand in the appended claims are by weight and all temperatures are in °C.

    ______________________________________                                        Component             Percent                                                 ______________________________________                                        *Dobanol ® 91/5 (Shell)                                                                         9.88                                                    **Dobanol 91/2.5 (Shell)                                                                            2.47                                                    Tripropylene glycol n-butyl ether                                                                   7.00                                                    ***Aerosol ® OT 100 (Cyanamid)                                                                  0.65                                                    Water, deionized      75.00                                                   ****Isopar ® H (Exxon)                                                                          5.00                                                                          100.00                                                  ______________________________________                                         *C.sub.9-11 fatty alcohol condensed with 5 moles of ethylene oxide per        mole                                                                          **C.sub.9-11 fatty alcohol condensed with 2.5 moles of ethylene oxide per     mole                                                                          ***Di(2-ethylhexyl) sodium sulfosuccinate                                     ****C.sub.10-11 isoparaffin                                              

The above composition and corresponding compositions in which thetripropylene glycol n-butyl ether is replaced by dipropylene glycoln-butyl ether and propylene glycol n-butyl ether are made by mixingtogether the nonionic surfactants, dissolving them in the water or aportion of the water, dissolving the anionic surfactant in the aqueousnonionic surfactant solution or in another portion of the water, mixingtogether such aqueous portions if separate dissolvings were practiced,admixing the cosurfactant with the aqueous surfactant solution andfinally, admixing the lipophile with the balance of the composition.Such formulation is done at room temperature (25° C.) and is effected ina short time, such as 5 to 10 minutes. The result is a clear liquidcrystal detergent composition of the formula of the X identified bynumeral 23 in FIG. 1 (when tripropylene glycol n-butyl ether is thecosurfactant). When propylene glycol n-butyl ether is the cosurfactantthe composition is within the liquid crystal area of the phase diagramof FIG. 2, with the point indicated by numeral 37 identifying it.

The compositions made, all of which are in clear liquid crystal form,are tested for soil removal properties (cleaning effectiveness) inpre-spotting and washing applications against soils that are present onhard surfaces, such as tile walls and dishes, and on fabrics, such assoiled laundry, and are compared to commercial liquid detergents andpre-spotting agents for cleaning actions. In the following laboratorytests the invented compositions are compared to commercial liquid andpaste pre-spotting agents and to unbuilt liquid detergent compositions.For hard surface treatments, to simulate cleanings of soils from walls,such as tile and Formica® walls, and tile and linoleum floors, threetests were run. In the first of these white Formica tiles are uniformlysprayed with a chloroform solution of a mixture of hardened tallow, beeftallow and oil soluble red dye, and such soil is allowed to dry to roomtemperature for thirty minutes before inception of the test. Then, fivegram samples of each of the test compositions are weighed out intopre-wet sponges which have been wrung out to remove any excess water,and the cleaning actions of the products are tested on the describedsoiled tiles by utilization of a machine which moves the sponge over thetiles and counts the strokes required to clear a path through the soilto the tile surface. The invented compositions take ten strokes andcommercial products take 25 to 40 strokes, e.g., 33 strokes. From pastexperience a five stroke difference is significant so in the presentcase the difference found is more than four times that significantnumber, showing that the invented compositions are very much better incleaning hard surfaces stained with fatty material (animal fats).

The second test employed is a pre-spotting type application of thecleaning compositions to white enamel tile surfaces onto which therehave been brushed chloroform solutions of tar. In such tests 2.5 gramsof a 10% tar solution is painted onto each tile surface and is allowedto dry to room temperature for five minutes. 0.5 Gram of each of thetest compositions is applied to different sections of the tile andallowed to remain in contact therewith for one minute, after which thetile is rinsed under cold (15° C.) tap water and the extents of tarremovals are noted. The invented liquid crystal compositions remove allthe tar but the commercial liquid detergents do not remove any of it, inthese tests. In the third set of experiments white enamel tiles arepainted with a solution of used motor oil, linseed oil, hardened tallowand varnish in petroleum ether and the soil coating is baked onto thetiles in an oven at 300° C. for ten minutes. 0.5 Gram of each of thetest compositions is then weighed out onto the soiled tiles and suchcompositions are allowed to remain in contact with the soils for thirtyminutes, after which they are rinsed off under cold tap water and soilremoval is visually evaluated. In such tests the same results areobtained as in the second set of tests, with the invented compositionsbeing far superior to the commercial preparations.

In another set of hard surface treatment experiments, intended tosimulate removals of soils from dishes, five different types of soilsare prepared, painted onto dishes and baked onto them. The soils are: aburnt fatty soil, comprising peanut oil, corn oil, meat (beef) extractand ground cherries; burnt milk; vermicelli with cheese; mashedpotatoes; and burnt cream sauce. Such soils are applied to Pyrex®dishes, stainless steel pans, glass pans, enamelled pans and Pyrexdishes, respectively. The various compositions are applied to thedifferent soils and allowed to stand on them for periods from 30 minutesto an hour, with the "standing times" being the same for eachcomparison. Then the substrates are subjected to rinsing with water andsometimes are subjected to light sponging, but again, the varioustreatments are conducted under the same conditions so as to becomparative and meaningful. The rinsed items are then allowed to dry,are observed, and soil removals are comparatively estimated by a panelof observers. In all cases the invented products are found to be betterin soil removal and the panel significantly prefers them over commercialliquid detergents applied either in neat (100%) or 20% aqueous solutionform.

The invented liquid crystal detergent compositions are compared to acommercial pre-spotting agent in paste form, which contains moresynthetic organic detergent, and also contains builder salt (sodiumtripolyphosphate). Different cotton swatches are stained with EMPA soil(vegetable oil and dust), Spangler soil (animal and vegetable oils andfats), wine, tomato sauce, cherries, chocolate ice cream, blood anddirty motor oil. The soils are applied to cotton swatches and theswatches are dried at 180° C. before use. Before beginning the cleaningtests, the swatches are read on a reflectometer and similar Rd readingsare taken at the completions of the tests. The pre-spotting operationsinvolve applying two grams of each neat product onto the swatches,leaving the products incontact with the soiled swatches for 30 minutes,rinsing and drying, after which the swatches are again read, using thereflectometer. From such readings the percentages of soil removals arecalculated. It is found that the invented liquid crystal detergentcomposition, without builder salt and with less detergent content thanthe paste pre-spotting agent, is equivalent to it or better in removingall stains except blood, in which the commercial pre-spotter issignificantly better, but the invented compositions are better than thecommercial agent in removing fruit stains (cherries).

In addition to the laboratory experiments, practical use testcomparisons with commercial liquid detergents and pre-spotting agentsare undertaken by applying the same weights of experimental and thecomparative products to dirty painted wall surfaces, from which theproducts are lightly sponged after one minute and after three minutes.In such cases the invented liquid crystal detergent compositions adherebetter to the wall than do the other products, when the same weights ofall are sprayed onto the wall, using a hand sprayer, and the removals ofthe soils are noticeably better using the experimental products. Theexperimental products do not run soon after applications, as do thecomparative products, although they do thin out after changing tomicroemulsion form, which signals that cleaning has been effected.

In practical dishwashing and laundering tests the experimental andcomparative pre-spotting liquid detergent products are applied byspraying onto dirty dishes and onto soiled laundry, at the loci of thesoils, after which they are allowed to stay on such surfaces for fiveminutes and are then washed, using commercial dishwashing liquid orliquid laundry detergent, respectively. In such instances the soilremovals are better when the experimental products are utilized aspre-spotting agents. Similar results are obtainable when instead ofemploying commercial products for the washing operations, theexperimental products are used instead.

The results reported above are also obtainable when the experimentalcompositions include functional and aesthetic adjuvants, such aspreservatives, perfumes and colorants, for example 0.08% of formalin,0.45% of perfume and 0.008% of dye, and when NRE's replace BRE's asnonionic detergents.

    ______________________________________                                        Component            Percent                                                  ______________________________________                                        Dobanol 91/5         29.6                                                     Dobanol 91/2.5       7.4                                                      Sodium dioctyl sulfosuccinate                                                                      2.0                                                      Tripropylene glycol n-butyl ether                                                                  21.0                                                     C.sub.10-11 isoparaffin                                                                            15.0                                                     Water, deionized     25.0                                                                          100.0                                                    ______________________________________                                    

The above described liquid crystal detergent composition is a clearwater-in-oil microemulsion detergent that is made by mixing thecomponents thereof in the same manner as described in Example 1. Suchmicroemulsion, like the other microemulsions resulting from employmentsof the invented liquid crystal compositions, is dilutable with roomtemperature water (and even cold water). In tests like those reported inExample 1 it also performs exceptionally well, being an acceptablelaundry pre-spotter and being far superior to liquid dishwashingdetergent compositions and other liquid detergent compositionscommercially employed for cleaning walls, floors, tiles and dishes.

EXAMPLE 3

Concentrates of the formulas represented by points 25 (FIG. 1) and 33(FIG. 2) are made in the manner described in Example 1 and are convertedby dilution with water to liquid crystal detergent compositions of theformulas described by points 27 and 23 (FIG. 1) and 37 (FIG. 2),respectively. Of course, for the FIG. 2 formulas propylene glycoln-butyl ether is substituted for the tripropylene glycol n-butyl etherof the FIG. 1 formula. If desired, the concentrate formulas of points 27and 33 are employed directly as pre-spotting agents or as detergentcompositions, with satisfactory results but it is usually preferred todilute them to liquid crystal form before use.

EXAMPLE 4

Variations of the preceding working example formulas may be made inwhich the proportions of components are adjusted ±10, ±20 and ±30%,while remaining within the ranges given in the specification, andessentially the same desirable pre-spotting and cleaning results areobtainable. Similarly, there may be substituted for the indicatednonionic detergents, anionic surfactant, cosurfactant and lipophile,other such compounds, as set forth in the specification, such asNeodol®25-3, potassium dihexyl sulfosuccinate, triethylene glycolisobutyl ether and n-decane and/or methyl cocoate. Mixtures of thevarious individual components may also be employed in some cases toproduce optimum results. Although usually builder salts will be omittedfrom the present formulations, so as to make the products useful forpre-spotting and washing of dishes, as well as laundry and wall andfloor surfaces, for those products not intended for hand dishwashingapplications such builder salts may be present, such as sodiumtripolyphosphate and sodium carbonate, so long as they do not interferewith the desirable liquid crystal state of the product and thespontaneous transformation of such product to microemulsion state inuse. The builder content will usually be held to no more than 10%,preferably to no more than 5%.

The various advantages of the invention have already been set forth insome detail and will not be repeated here. However, it will bereiterated that the invention relates to the important discovery thateffective liquid detergent compositions can be made in the liquidcrystal state and that because they are in such state they areespecially effective in removing lipophilic soils from substrates andalso are effective in removing from substrates non-lipophilic soilswhich are bound to the substrates by lipophilic materials. Suchdesirable properties of the liquid crystal detergent compositions ofthis invention make them ideal for use as pre-spotting agents anddetergents for removing hard-to-remove soils from substrates in varioushard and soft surface cleaning operations. Especially important is thespontaneous conversion of the invented compositions to microemulsionform, during which conversion lipophilic soil is loosened and absorbedfrom the soiled substrate without the need for applications ofsignificant amounts of energy, either in thermal or mechanical form.Thus, the invention is a significant one and represents an importanttechnical advance in the art.

The invention has been described with respect to various embodiments andillustrations of it but is not to be considered as limited to thesebecause it is evident that one of skill in the art with the presentspecification before him or her will be able to utilize substitutes andequivalents without departing from the invention.

What is claimed is:
 1. A liquid crystal detergent composition consisting essentially of:(a) about 5 to about 40 wt. % of a mixture of an anionic surfactant or cationic surfactant and a nonionic surfactant with the amount of the anionic surfactant or of the cationic surfactant being about 2 to 25 wt. % of the amount of the nonionic surfactant, said anionic surfactant being a C₄₋₁₂ alcohol ester of a sulfosuccinic add salt, said nonionic being a condensation product of one mole of higher fatty alcohol of 9 to 11 carbon atoms with 2 to 6; moles of ethylene oxide and said cationic surfactant being a quaternary ammonium halide; (b) about 0.5 to about 20 wt. % of a cosurfactant which is a monoalkyl ether of a lower glycol or polyalkylene glycol of the formula RO(x)_(n) H, wherein R is a C₁₋₅ alkyl group, n is from 1 to 5 and x is CH₂ CH₂ O or CH(CH₃)CH₂ O; (c) about 1 to about 20 wt. % of a lipophilic solvent selected from the group consisting of a paraffin having 9 to 11 carbon atoms and an ester of a higher alcohol and lower carboxylic acid and an ester of a lower alcohol and a higher carboxylic acid; and (d) about 40 to 90 wt. % of water, said liquid crystal detergent composition having a storage modules at 25° C. equal to or higher than one Pascal.
 2. A liquid crystal composition according to claim 1 wherein the lipophilic solvent is said paraffin having 9 to 11 carbon atoms.
 3. A liquid detergent composition according to claim 1 the figure of which is within the liquid crystal area designated by numeral 13 of FIG.
 1. 4. A process for treating materials soiled with lipophilic soil to loosen or remove it which comprises applying to the locus of such soft on such material a soil loosening or removing amount of a composition according to claim
 1. 5. A process according to claim 4 wherein the composition is applied as a pre-treatment to material soiled with hard-to-remove lipophilic soil at the locus thereof on the material, after which application the soil is removed by application of the same or a different detergent composition and water.
 6. A process according to claim 5 wherein the composition is applied as a pre-treatment onto dishes having deposits of animal fat thereon before hand washing of such dishes in dishwater containing a dishwashing detergent composition.
 7. A process according to claim 5 wherein the composition is applied as a pre-spotting treatment onto laundry soiled with oily or greasy soils at the loci of such soils before washing of the laundry in wash water containing a laundry detergent composition.
 8. A process for treating material soiled with lipophilic soil to loosen or remove it which comprises applying to the locus of such soil on such material a soil loosening or removing amount of a composition according to claim
 3. 9. A process according to claim 7 wherein the composition is applied as a pre-treatment on materials soiled with hard-to-remove lipophilic soil at the locus thereof on the material, after which application the soil is removed by application of the same or a different detergent composition and water.
 10. A process according to claim 9 wherein the composition is applied as a pre-treatment onto dishes having deposits of animal fat thereon before washing of such dishes in dishwater containing a dishwashing detergent composition. 